Arthropodicidal and nematocidal phosphoramidates

ABSTRACT

This invention relates to novel phosphoramidates of the formula: ##STR1## wherein R 1  is (C 6  -C 10 ) aryl optionally substituted with alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, dialkylamino, haloalkyl, hydroxyalkyl, cyano, nitro, hydroxy, or halogen; 
     R 2  is hydrogen.[., alkyl, cycloalkyl, alkenyl, or optionally substituted aralkyl or aryl.]. 
     R 3  is (C 1  -C 6 ) alkyl; 
     R 4  is (C 3  -C 4 ) alkyl; .Iadd.X is sulfur; .Iaddend.and 
     .[.X,.]. Y and Z are independently oxygen or sulfur; 
     and the agronomically acceptable metal salts and metal salt complexes thereof; to compositions containing them; and to methods of using them to control certain harmful pests, e.g. arthropods and nematodes.

This invention relates to novel phosphoramidates, to compositionscontaining them, and to methods of using them to control certain harmfulpests.

The novel compounds of this invention can be represented by the formula:##STR2## wherein R¹ is a (C₆ -C₁₀) aryl, preferably phenyl, group,optionally substituted with up to five, but preferably up to three, (C₁-C₄) alkyl groups, (C₁ -C₄) alkoxy groups, (C₁ -C₄) alkylthio groups,(C₁ -C₄) alkylsulfinyl groups, (C₁ -C₄) alkylsulfonyl groups, di-(C₁-C₄) alkylamino groups, (C₁ -C₄) haloalkyl groups, (C₁ -C₄) hydroxyalkylgroups, cyano groups, nitro groups, hydroxyl groups, or halogen atoms;

R² is

.[.(a).]. a hydrogen atom;

.[.(b) a (C₁ -C₁₀) alkyl group, preferably a (C₁ -C₄) alkyl group.].

.[.(c) a (C₃ -C₈) cycloalkyl group, preferably a (C₅ -C₇) cycloalkylgroup.].

.[.(d) a (C₃ -C₆) alkenyl group, preferably a (C₃ -C₄) alkylenylgroup.].

.[.(e) an optionally substituted aralkyl group of up to 11 carbon atoms,preferably an unsubstituted benzyl group; or.].

.[.(f) an optionally substituted (C₆ -C₁₀) aryl group, preferably anunsubstituted phenyl group.].

R³ is a (C₁ -C₆) alkyl group, preferably a (C₁ -C₄) alkyl group;

R⁴ is a (C₃ -C₄) alkyl group;

X is .[.an oxygen or.]. .Iadd.a .Iaddend.sulfur atom;

Y is an oxygen or sulfur atom, preferably an oxygen atom; and

Z is an oxygen or sulfur atom, preferably an oxygen atom;

and the agronomically acceptable metal salts and metal salts complexesthereof.

The metal salts of this invention are the alkali and alkaline earthmetal salts of the compounds of Formula I. The preferred metal salt isthe sodium salt.

The metal salt complexes of this invention are represented by thefollowing formula which is presented for illustrative purposes only:##STR3## wherein R¹, R², R³, R⁴, X, Y, and Z are as defined for FormulaI;

M is a metal cation which can be selected from groups IIA, IIA, IB, IIB,VIIB, and VIII of the periodic table;

W is an anion such as chloride, bromide, iodide, sulfate, bisulfate,phosphate, nitrate, perchlorate, carbonate, bicarbonate, hydroxide,acetate, oxalate, malate, citrate, and the like;

m is an integer of 1-2;

m' is an integer of 1-2; and

m" is an integer of 0-4.

Among the compounds depicted by Formula II above, the preferredcompounds are those wherein the metal cation is a transition metal suchas copper, zinc, nickel, cobalt, tin, cadmium, or manganese; or analkaline earth metal such as calcium or magnesium, and wherein the anionis chloride, bromide, nitrate, sulfate or hydroxide. The most preferredsalts are those wherein the metal cation is copper, zinc, nickel,cobalt, tin, cadmium or manganese, and the anion is hydroxide.

In Formulas I and II above, R² is preferably a hydrogen atom.

The preferred compounds of this invention possess especially enhancednematocidal and arthropodicidal (e.g. acaricidal and insecticidal)activity, and can be represented by the formula: ##STR4## wherein A isindependently:

(a) a (C₁ -C₄) alkyl group, preferably a methyl group;

(b) a (C₁ -C₄) alkoxy group, preferably a methoxy group;

(c) a (C₁ -C₄) alkylthio group, preferably a methylthio group;

(d) a di-(C₁ -C₄) alkylamino group, preferably a dimethylamino group;

(e) a trihalomethyl group, preferably a trifluoromethyl group; or

(f) a halogen atom, preferably a chlorine atom;

R⁵ is a (C₁ -C₄) alkylthio group, preferably a propylthio group, or a(C₁ -C₄) alkoxy group, preferably an ethoxy group;

R⁶ is a (C₃ -C₄) alkyl group, preferably a n-propyl group, an isobutylgroup, or a sec-butyl group;

X' is .[.an oxygen or.]. .Iadd.a .Iaddend.sulfur atom, preferably anoxygen atom; and

n is an integer from 0 to 3, preferably from 0 to 2;

and the agronomically acceptable metal salts and metal salt complexesthereof;

Among the preferred compounds, the most preferred are compounds whereinR⁵ is an ethoxy group and R⁶ is an isobutyl group or a sec-butyl group.

As used in the specification and claims, the terms alkyl, alkenyl,alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkyl,hydroxyalkyl, dialkylamino, and aralkyl, are meant to include branchedas well as straight chain groups.

Representative R¹ substituents include, for example, phenyl,2-chlorophenyl, 3,4-dichlorophenyl, 2,4,6-trichlorophenyl,4-bromophenyl, 4-bromo-2-chlorophenyl, 4-fluorophenyl,3-trifluoromethylphenyl, 4-chloroethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2-chloro-4-methylphenyl,2,4-dichloro-3,5-dimethylphenyl, 2-ethyl-4-methoxyphenyl, 4-butylphenyl,3-methylthiophenyl, 4-methylsulfinylphenyl, 4-methylsulfonylphenyl,5-methoxyphenyl, 2-ethoxyphenyl, 4-diethylaminophenyl, 4-nitrophenyl,2-chloro-4-nitrophenyl, 2-cyanophenyl, 2,4-dihdroxyphenyl,4-hydroxybutylphenyl, naphthyl, 4,6-dichloronaphthyl, 2-methylnaphthyl,3-methyl-5-methoxynaphthyl, 3,5-ditrifluoromethylnaphthyl, and the like.

.[.Representative R² substituents include, for example, hydrogen,methyl, butyl, isopropyl, hexyl, cyclopentyl, cyclohexyl, allyl,3-butenyl, 4-methyl-2-pentenyl, phenyl, 4-nitrophenyl,3,5-dichlorophenyl, benzyl, 3,5-dimethylbenzyl, 4-chlorobenzyl,phenethyl, α-methylbenzyl, naphthyl, 3-methylnaphthyl,3,5-dichloronaphthyl, and the like..].

Representative R³ substituents include, for example, methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl, neopentyl, pentyl, hexyl,and the like.

Examples of the compounds embraced by this invention include:

S-(1-methylpropyl) N-phenylaminothiocarbonyl O-propylphosphoramidothioate

.[.O,S-dipropyl N-methyl N-phenylaminothiocarbonylphosphoramidothioate.].

.[.O-butyl S-(2-methylpropyl) N-phenyl N-phenylaminothiocarbonylphosphoramidothioate.].

O-ethyl N-(2-methylphenyl)aminothiocarbonyl S-(1-methylpropyl)phosphoramidothioate

O-ethyl N-(4-methoxyphenyl)aminothiocarbonyl S-methylethylphosphoramidothioate

O-ethyl S-(1-methoxypropyl) N-(2-methylthiophenyl)aminothiocarbonylphosphoramidothioate

O-ethyl S-(2-methylpropyl) N-(4-methylsulfonylphenyl)aminothiocarbonylphosphoramidothioate

O-ethyl S-(1-methylpropyl) N-(4-ethylsulfinylphenyl)aminothiocarbonylphosphoramidothioate

O-ethyl N-(3-methyl-4-methylthiophenyl)aminothiocarbonylS-(1-methylpropyl) phosphoramidothioate

.[.N-allyl O-ethyl S-(1-methylpropyl) N-(4-nitrophenyl)aminothiocarbonylphosphoramidothioate.].

N-(4-cyanophenyl)aminothiocarbonyl O-ethyl S-(1-methylpropyl)phosphoramidothioate

N-(4-diethylaminophenyl)aminothiocarbonyl O-ethyl S-(1-methylpropyl)phosphoramidothioate

N-(3,5-dibromophenyl)aminothiocarbonyl O-ethyl S-propylphosphoramidothioate

.[.N-(3,5-dichlorophenyl)aminothiocarbonyl O-ethyl N-(4-methylbenzyl)S-(1-methylpropyl) phosphoramidothioate.].

N-(2-bromo-4-chlorophenyl)aminothiocarbonyl O-ethyl S-methylethylphosphoramidothioate

S-butyl N-(3,5-dichlorophenyl)aminothiocarbonyl O-ethylphosphoramidothioate

N-(2,4-dichlorophenyl)aminothiocarbonyl O-methyl S-(1-methylpropyl)phosphoramidothioate

N-(3,4-dichlorophenyl)aminothiocarbonyl O-hexyl S-(1-methylpropyl)phosphoramidothioate

N-(3,5-dichlorophenyl)aminothiocarbonyl S,S-dipropylphosphoramidodithioate

N-(2,4-dichlorophenyl)aminothiocarbonyl S,S-bis-(1methylpropyl)phosphoramidotrithioate

O-ethyl S-(1-methylpropyl) N-(2,4,6-trichlorophenyl)aminothiocarbonylphosphoramidothioate

N-(3,5-ditrifluoromethylphenyl)aminothiocarbonyl O-ethylS-(2-methylpropyl) phosphoramidothioate

O-ethyl N-(2-hydroxyphenyl)aminothiocarbonyl S-(1-methylpropyl)phosphoramidothioate

O-ethyl N-(2-hydroxymethylphenyl)aminothiocarbonyl S-(1-methylpropyl)phosphoramidothioate

O-ethyl S-(1-methylpropyl) N-(2-naphthyl)aminothiocarbonylphosphoramidothioate

O-ethyl S-methylethyl N-[1-(3-trifluoromethyl)naphthyl]aminothiocarbonylphosphoramidothioate

.[.O-ethyl S-methylpropyl) N-phenylaminocarbonyl phosphoramidothioate.].

.[.N-benzyl O-ethyl S-(1-methylpropyl) N-phenylaminocarbonylphosphoramidothioate.].

.[.S,S-dipropyl N-phenylaminocarbonyl phosphoramidothioate.].

.[.N-(2,4-dimethylphenyl)aminocarbonyl O-ethyl S-(1-methylpropyl)phosphoramidothioate.].

.[.O-ethyl S-(1-methylpropyl) N-(4-propylthiophenyl)aminocarbonylphosphoramidothioate.].

.[.N-(3,4-dichlorophenyl)aminocarbonyl S,S-dipropylphosphoramidotrithioate.].

.[.N-(2,4-dichlorophenyl)aminocarbonyl S-ethyl N-methylethyl S-propylphosphoramidodithioate.].

.[.N-(2,3,4,5,6-pentachlorophenyl)aminocarbonyl O-ethyl S-propylphosphoramidothioate.].

.[.O-ethyl N-(4-fluorophenyl)aminocarbonyl S-propylphosphoramidothioate.].

.[.N-(4-chloro-2-methylphenyl)aminocarbonyl O-ethyl S-(1-methylpropyl)phosphoramidothioate.].

.[.N-(4-chloromethylphenyl)aminocarbonyl S-(1-methylpropyl) O-propylphosphoramidothioate.].

.[.N-(2-butenyl) N-3,5-ditrifluoromethylphenyl)aminocarbonyl O-ethylS-propyl phosphoramidothioate.].

.[.N-(4-cyano-2-nitrophenyl)aminocarbonyl O-ethyl S-(1-methylpropyl)phosphoramidothioate.].

.[.N-(4-chlorophenyl)aminocarbonyl N-(4-cyanophenyl) O-ethylS-(1-methylpropyl) phosphoramidothioate.].

.[.O-ethyl S-(1-methylpropyl) N-(2-naphthyl)aminocarbonylphosphoramidothioate.].

.[.S,S-dipropyl N-(1-naphthyl)aminocarbonyl phosphoramidodithioate.].

.[.N-[1-(5,7-dichloronaphthyl)aminocarbonyl] O-ethyl S-(2-methylpropyl)phosphoramidothioate.].

.[.S-butyl O-methyl N-[1-(3-methylnaphthyl)aminocarbonyl]phosphoramidothioate.].

.[.N-[2-(5,7-dinitronaphthyl)aminocarbonyl] O-ethyl S-propylphosphoramidothioate.].

and the agronomically acceptable metal salts and metal salt complexesthereof, and the like.

The phosphoramidates of this invention are prepared by various methods.One method involves contacting an appropriate aromatic amine with anappropriately substituted phosphoroisothiocyanate orphosphoroisocyanate. This reaction can be represented by the followingequation: ##STR5## wherein R¹, R³, R⁴, X, Y, and Z are as defined forFormula I.

The reaction is generally carried out in the presence of an aproticsolvent such as glyme, acetone, acetonitrile, ethyl acetate, butylacetate, diethyl ether, or mixtures thereof, at a temperature range ofabout 15° to about 120° C., preferably at about 25° to about 45° C. Asubstantially equimolar ratio of reactants is preferred, but an excessof phosphoroisothiocyanate or isocyanate can be used. The desiredproduct can be separated from the reaction mixture by conventionalmeans, such as fractional crystallization, chromatography, extraction orthe like.

.[.Another method for preparing compounds within the scope of thisinvention involves contacting an appropriate aromatic amine with anappropriately substituted chloro(thio)carbonyl phosphoramidate. Thisreaction can be represented by the following equation:.]. ##STR6##.[.wherein R¹, R², R³, R⁴, X, Y, and Z are as defined for Formula I,with the exception that R² may not be hydrogen..].

.[.This reaction is generally carried out in the presence of an aproticsolvent such as glyme, acetone, acetonitrile, ethyl acetate, butylacetate, diethyl ether, or mixtures thereof, at a temperature range ofabout 15° to about 120° C., preferably at about 25° to about 45° C. Anacid acceptor such as a tertiary amine can be employed as a scavenger inthis preparation. Representative acid acceptors include pyridine,trimethylamine, triethylamine, and the like. However, an excess of theamine reactant can also serve as the acid acceptor. Generally, asubstantially equimolar ratio of reactants is preferred, but an excessof two or more moles of amine can be employed if the amine is intendedto serve the dual function of reactant and acid acceptor. The desiredproduct can be separated from this reaction mixture by conventionalmeans..].

.[.A third.]. .Iadd.Another .Iaddend.method of preparing compounds ofthis invention involves contacting an appropriate phosphoramidate withan appropriate isocyanate or isothiocyanate. This reaction can berepresented by the following equation: ##STR7## wherein R¹, R², R³, R⁴,X, Y, and Z are as defined for Formula I.

The reaction is generally carried out in the presence of an aproticsolvent such as glyme, acetone, acetonitrile, ethyl acetate, butylacetate, diethyl ether, or mixtures thereof, at a temperature range ofabout 20° to about 60° C., room temperature being preferred. Asubstantially equimolar ratio of reactants is preferred. The desiredproduct can be separated from the reaction mixture by conventionalmeans.

The metal salts of this invention are prepared by (1) adding an alkalior alkaline earth metal hydroxide or hydride to a suspension of thephosphoramidate in a suitable solvent, (2) stirring the mixture until asolution forms, and (3) freeze drying the solution, or in thealternative, (4) concentrating the solution in vacuo at roomtemperature, and drying the residue in a vacuum oven at roomtemperature.

The metal salt complexes are prepared by (1) reacting, in an aqueous oralcoholic medium, a phosphoramidate of this invention, with a metal saltselected from group IIA, IIIA, IB, IIB, VIIB, or VIII of the periodictable, (2) filtering off the precipitate which forms, and (3) washingand drying the precipitate to give the product.

All of the starting materials used in the preparation of the compoundsof this invention are known compounds or are readily prepared by methodsavailable to those skilled in the art.

By way of demonstration, the following examples are offered toillustrate this invention and are not to be construed as limitationsthereof.

.[.EXAMPLE 1.]. .[.Preparation of O-ethyl S-(1-methylpropyl)N-phenylaminocarbonyl phosphoramidothioate.].

.[.To a solution of 0.93 g. (0.01 mole) of aniline in 5 ml. of glyme isadded 2.23 g. (0.01 mole) of O-ethyl S-(1-methylpropyl)phosphoroisocyanatothioate (exothermic reaction). The solution isallowed to stand at room temperature from 24 hours and then poured into250 ml. of water. The semi-solid precipitate is isolated and slurried in20 ml. of ether. The ethereal slurry is filtered and dried to afford0.35 g. (11%) of product..].

EXAMPLE 6 Preparation of O-ethyl N-(4-methylphenyl) aminothiocarbonylS-(1-methylpropyl) phosphoramidothioate

To a solution of 1.07 g. (0.01 mole) of 4-methylaniline in 5 ml. ofglyme is added 2.39 g. (0.01 mole) of O-ethyl S-(1-methylpropyl)phosphoroisocyanatothioate (exothermic reaction). The solution isallowed to stand at room temperature for six days and then poured intoan excess of water (300 ml.). The suspension which forms is vacuumfiltered. The filter cake is slurried in 50 ml. of hexane, filtered, anddried to afford 1.6 g. (47%) of product.

EXAMPLE 9 Preparation of O-ethyl N-(4-methylphenyl)aminothiocarbonylS-(1-methylpropyl) phosphoramidothioate

To a solution of 1.23 g. (0.01 mole) of 4-methoxyaniline in 5 ml. ofglyme is added 2.39 g. (0.01 mole) of O-ethyl S-(1-methylpropyl)phosphoroisothiocyanatothioate (exothermic reaction). The solution isallowed to stand at room temperature for 18 hours and then poured intoan excess of water. The suspension which forms is vacuum filtered andthe filter cake is slurried in 100 ml. of hexane, filtered, and dried toafford 2.4 g. (66.5%) of product.

EXAMPLE 10 Preparation of N-(4-dimethylaminophenyl)aminothiocarbonylO-ethyl S-(1-methylpropyl) phosphoramidothioate

To a solution of 1.36 g. (0.01 mole) of N,N-dimethyl-4-phenylenediaminein 5 ml. of glyme is added 2.39 g. (0.01 mole) of O-ethylS-(1-methylpropyl) phosphoroisothiocyanatothioate (exothermic reaction).The solution is allowed to stand at room temperature for 24 hours andthen poured into an excess of water. The precipitate which forms isslurried in hexane and then vacuum filtered. The filter cake isre-slurried in 15 ml. of ethyl acetate, vacuum filtered and dried toafford 0.9 g. (24.6%) of product.

EXAMPLE 14 Preparation of N-(3,5-dichlorophenyl)aminothiocarbonylO-ethyl S-propyl phosphoramidothioate

To a solution of 1.62 g. (0.01 mole) of 3,5-dichloroaniline in 5 ml. ofglyme is added 2.25 g. (0.01 mole) of O-ethyl S-propylphosphoroisothiocyanatothioate. The product is obtained by pouring thereaction solution into an excess of water, vacuum filtering thesuspension which forms, and recrystallizing the isolated precipitatefrom methylcyclohexane. The yield of product is 1.8 g. (47.5%).

EXAMPLE 15 Preparation of N-(3,5-dichlorophenyl)aminothiocarbonylO-ethyl S-methylethyl phosphoramidothioate

To a solution of 2.82 g. (0.0178 mole) of 3,5-dichloroaniline in 5 ml.of glyme is added 4 g. (0.0178 mole) of O-ethyl S-methylethylphosphoroisothiocyanatothioate. The solution is heated to reflux and isallowed to stand at room temperature for two hours. The suspension whichforms is vacuum filtered. The filter cake is washed with 10 ml. ofglyme, 20 ml. of ether, and dried to afford 2 g. (29%) yield of product.

EXAMPLE 17 Preparation of N-(3,5-dichlorophenyl)aminothiocarbonylO-ethyl S-(2-methylpropyl) phosphoramidothioate

To a solution of 1.62 g. (0.01 mole) of 3,5-dichloroaniline in 5 ml. ofglyme is added 2.39 g. (0.01 mole) of O-ethyl S-(2-methylpropyl)phosphoroisothiocyanatothioate. The solution is heated to reflux andallowed to stand at room temperature for three days. The solution ispoured into an excess of water and the semi-solid precipitate whichforms is isolated. The product is slurried in 50 ml. of hexane andvacuum filtered. The filter cake is dried to afford 1.8 g. (45%) ofproduct.

EXAMPLE 18 Preparation of N-(3,5-dichlorophenyl)aminothiocarbonylO-ethyl S-(1-methylpropyl) phosphoramidothioate

To a solution of 3.24 g. (0.02 mole) of 3,5-dichloroaniline in 15 ml. ofglyme is added 4.8 g. (0.02 mole) of O-ethyl S-(1-methylpropyl)phosphoroisothiocyanatothioate. The solution is allowed to stand at roomtemperature for 18 hours and then poured into an excess of water. Thesemi-solid precipitate which forms is isolated and slurried in 50 ml. ofhexane. The hexane slurry is filtered to afford 3.25 g. (40.5%) ofproduct, m.p. 123°-125° C. Recrystallization from methylcyclohexanegives 2.5 g. (31%) of product.

.[.EXAMPLE 23.]. .[.Preparation ofN-(3,5-ditrifluoromethylphenyl)aminothiocarbonyl O-ethylS-(1-methylpropyl) phosphoramidothioate

To a solution of 1.03 g. (0.0045 mole) of 3,5-ditrifluoromethylanilinein 5 ml. of glyme is added 1 g. (0.0045 mole) of O-ethylS-(1-methylpropyl) phosphoroisothiocyanatothioate (exothermic reaction).The solution which forms is allowed to stand at room temperature for11/2 hours and is poured into 200 ml of water. The suspension whichforms is vacuum filtered and the filter cake recrystallized frommethylcyclohexane to afford 0.92 g. (46%) of product..].

                                      TABLE I                                     __________________________________________________________________________     ##STR8##                                                                                                    ELEMENTAL ANALYSIS                             Compound                       Calculated (Found)                             Number                                                                              X"                                                                              R.sup.7   R.sup.8                                                                          R.sup.9                                                                           M.P., °C.                                                                    %C  %H  %N  %P  %S                             __________________________________________________________________________    .[.1  0 C.sub.6 H.sub.5                                                                        OC.sub.2 H.sub.o                                                                  C.sub.4 H.sub.9.sup.s                                                             74-77 49.35                                                                             6.69                                                                              8.86                                                                              9.79                                                                              --                                                            (49.22)                                                                           (6.84)                                                                            (8.64)                                                                            (9.60)                                                                            --.].                          2     S C.sub.6 H.sub.5                                                                        OC.sub.2 H.sub.5                                                                  C.sub.3 H.sub.7.sup.i                                                             9-101 45.43                                                                             5.98                                                                              8.84                                                                              9.94                                                                              19.67                                                         (45.26)                                                                           (6.03)                                                                            (8.80)                                                                            (9.73)                                                                            (20.14)                        .[.3  O C.sub.6 H.sub.4 CH.sub.3 -2                                                            OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.s                                                             oil   50.8                                                                              7.0 8.5 --  9.7                                                           (50.5)                                                                            (6.7)                                                                             (8.3)                                                                             --  (9.6)                          4     O C.sub.6 H.sub.4 CH.sub.3 -4                                                            OC.sub. 2 H.sub.5                                                                 C.sub.4 H.sub.9.sup.s                                                             75-80 51.0                                                                              6.7 8.5 --  --                                                            (50.7)                                                                            (7.1)                                                                             (.5)                                                                              --  --                             5     O C.sub.6 H.sub.4 CH.sub.34                                                              OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.s                                                             130-135                                                                             50.8                                                                              7.0 8.5 --  9.7                                                           (50.3)                                                                            (6.9)                                                                             (8.1)                                                                             --  (10.0).].                      6     S C.sub.6 H.sub.4 CH.sub.3 -4                                                            OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.s                                                             78-80 48.42                                                                             6.66                                                                              7.96                                                                              9.12                                                                              --                                                      dec.  (48.53)                                                                           (6.69)                                                                            (8.09)                                                                            (8.94)                                                                            --                             .[.7  O C.sub.6 H.sub.4 CH.sub.3 -4                                                            OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.i                                                             120-122                                                                             50.9                                                                              7.0 8.5 --  9.7                                                           (50.6)                                                                            (6.9)                                                                             (8.6)                                                                             --  (9.9)                          8     O C.sub.6 H.sub.4 SCH.sub.3 -4                                                           OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.s                                                             101-104                                                                             46.07                                                                             6.60                                                                              7.57                                                                              8.78                                                                              17.80                                                         (46.39)                                                                           (6.41)                                                                            (7.73)                                                                            (8.54)                                                                            (17.69).].                     9     S C.sub.6 H.sub.4 OCH.sub.3 -4                                                           OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.s                                                             80-83 46.00                                                                             6.23                                                                              7.41                                                                              8.46                                                                              --                                                      dec.  (46.39)                                                                           (6.40)                                                                            (7.73)                                                                            (8.55)                                                                            --                             10    S C.sub.6 H.sub.4 N(CH.sub.3).sub.2 -4                                                   OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.s                                                             99-103                                                                              48.00                                                                             7.15                                                                              11.20                                                                             8.23                                                                              --                                                      dec.  (47.98)                                                                           (6.98)                                                                            (11.19)                                                                           (8.25)                                                                            --                             .[.11 O C.sub.6 H.sub.4 NO.sub.2 -4                                                            OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.s                                                             108-112                                                                             43.3                                                                              5.6 11.6                                                                              --  --                                                            (43.1)                                                                            (5.5)                                                                             (11.6)                                                                            --  --.].                          12    S C.sub.6 H.sub.4 Cl-4                                                                   OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.s                                                             83-85 42.71                                                                             5.59                                                                              7.43                                                                              8.35                                                                              --                                                            (42.56)                                                                           (5.50)                                                                            (7.64)                                                                            (8.44)                                                                            --                             .[.13 O C.sub.6 H.sub.4 Cl-4                                                                   OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.s                                                             89-93 43.35                                                                             5.74                                                                              7.59                                                                              --  --                                                      dec.  (44.51)                                                                           (5.75)                                                                            (7.99)                                                                            --  --.].                          14    S C.sub.6 H.sub.2 Cl.sub.2 -3,5                                                          OC.sub.2 H.sub.5                                                                  C.sub.3 H.sub.7                                                                   122-124                                                                             37.18                                                                             4.54                                                                              7.33                                                                              --  --                                                            (37.21)                                                                           (4.43)                                                                            (7.23)                                                                            --  --                             15    S C.sub.6 H.sub.3 Cl.sub.2 -3,5                                                          OC.sub.2 H.sub.5                                                                  C.sub.3 H.sub.7                                                                   138.5-141                                                                           37.35                                                                             4.43                                                                              7.10                                                                              7.98                                                                              --                                                            (37.21)                                                                           (4.43)                                                                            (7.23)                                                                            (8.00)                                                                            --                             16    S C.sub.6 H.sub.3 Cl.sub.2 -3,5                                                          OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9                                                                   93-96 38.61                                                                             4.84                                                                              6.86                                                                              --  --                                                            (38.90)                                                                           (4.77)                                                                            (6.98)                                                                            --  --                             17    S C.sub.6 H.sub.3 Cl.sub.2 -3,5                                                          OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.i                                                             108-111                                                                             38.90                                                                             4.70                                                                              6.84                                                                              7.70                                                                              --                                                            (38.90)                                                                           (4.77)                                                                            (6.98)                                                                            (7.72)                                                                            --                             18    S C.sub.6 H.sub.3 Cl.sub.2 -3,5                                                          OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.s                                                             130-131                                                                             39.02                                                                             4.87                                                                              7.08                                                                              --  --                                                            (38.90)                                                                           (4.77)                                                                            (6.98)                                                                            --  --                             19    .[.O                                                                            C.sub.6 H.sub.3 Cl.sub.2 -3,5                                                          OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.s                                                             144.5-147                                                                           40.18                                                                             5.06                                                                              6.99                                                                              7.93                                                                              --                                                      dec.  (40.53)                                                                           (4.97)                                                                            (7.27)                                                                            (8.04)                                                                            --.].                          20    S C.sub.6 H.sub.3 Cl.sub.23,5                                                            SC.sub.3 H.sub.7                                                                  C.sub.3 H.sub.7                                                                   89-91 37.21                                                                             4.62                                                                              6.60                                                                              7.42                                                                              --                                                      dec.  (37.41)                                                                           (4.59)                                                                            (6.71)                                                                            (7.42)                                                                            --                             21    S C.sub.6 H.sub.3 Cl.sub.2 -2,4                                                          OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.s                                                             82-84 38.99                                                                             4.81                                                                              6.75                                                                              7.79                                                                              --                                                            (38.90)                                                                           (4.77)                                                                            (6.98)                                                                            (7.72)                                                                            --                             22    S C.sub.6 H.sub.3 (CF.sub.3).sub.2 -3,5                                                  OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.s                                                             125.5-123.5                                                                         38.16                                                                             4.15                                                                              5.92                                                                              6.54                                                                              --                                                            (38.46)                                                                           (4.09)                                                                            (5.98)                                                                            (6.61)                                                                            --                             23    .[.O                                                                            C.sub.6 H.sub.3 (CF.sub.3).sub.2 -3,5                                                  OC.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9.sup.s                                                             162-164.5                                                                           40.36                                                                             4.52                                                                              6.19                                                                              --  --                                                            (39.82)                                                                           (4.23)                                                                            (6.19)                                                                            --  --                             24    O C.sub.6 H.sub.3 (CF.sub.1).sub.2 -3,5                                                  OC.sub.2 H.sub.5                                                                  C.sub.3 H.sub.7.sup.i                                                             183-185                                                                             38.19                                                                             4.20                                                                              6.33                                                                              6.99                                                                              7.52                                                          (38.86)                                                                           (3.92)                                                                            (6.39)                                                                            (7.06)                                                                            (7.31).].                      25    S C.sub.6 H.sub.3 (CF.sub.3).sub.23,5                                                    OC.sub.2 H.sub.5                                                                  C.sub.3 H.sub.7.sup.i                                                             127-128                                                                             37.00                                                                             3.86                                                                              6.00                                                                              6.74                                                                              14.47                                                         (37.00)                                                                           (3.78)                                                                            (6.14)                                                                            (6.82)                                                                            (14.11)                        __________________________________________________________________________     .sup.i = iso                                                                  .sup.s = secondary                                                       

The present compounds and the metal salts and metal salt complexesthereof (hereinafter collectively referred to as compounds orphosphoramidates) are useful for the protection of plants and animals,including man, from the ravages of harmful and annoying pests. Thesecompounds are particularly effective against nematodes and arthropods invarying stages of development. As arthropodicides, the compounds of thisinvention are especially effective against members of the classArachnoidea, which includes the Order Acarina, as represented by mitesand ticks, and the class Insecta, the insects. Among the arthropods andnematodes which are effectively controlled by the compounds of thepresent sent invention are the chewing insects, e.g. the southernarymworm (Spodoptera eridania), the sucking insects, e.g. the greenpeach aphid (Myzus persicae), soil-dwelling insects, e.g. the southerncorn rootworm (Diabrotica undecimpunctata howardi), houseflies, mites,e.g. the two-spotted spider mite (Tetranychus urticae), the southernroot knot nematode (Meloidogyne incognita), and others. Certaincompounds of this invention are also active as anthelmintics.

Generally, control of pests is achieved in accordance with thisinvention by application of the compounds of this invention inpesticidally effective amounts (e.g. arthropodically or nematocidallyeffective amounts) either directly to the pests to be controlled or tothe loci to be protected from attack by such pests. For example, food,fiber, forage, forest, and ornamental crops and stored products thereofwould represent plant protection loci. Treatment with the compounds ofthis invention of domestic animals, man and their immediate environssimilarly constitute representative loci for protection against variousannoying ectolparasitic or endoparasitic Acarina (Acari) and Insecta.Accordingly, compounds of the present invention provide utility as theessential active ingredient of pesticidal compositions suitable foragricultural and sanitary purposes.

The term "control" as employed in the specification and claims of thisapplication is to be construed as any means which adversely effects theexistence or growth of any living organism. Such means can comprise acomplete killing action, eradication, arresting in growth, repulsion,inhibition, reduction in number, or any combination thereof.

For use as pesticides, the compounds of this invention can be used assolutions, suspensions, or mixtures, in organic solvents orformulations. For example, they can be formulated as wettable powders,emulsifiable concentrates, dusts, granular formulations or flowableemulsifiable concentrates. In such formulations, the phosphoramidatesare present at a concentration of about 0.00001 to about 99%, preferablyabout 1 to about 95%, and are extended with an agronomically acceptableliquid or solid carrier. When desired, suitable surfactants are likewiseincorporated. Surfactants commonly used in the art can be found in theJohn W. McCutcheon, Inc. publication "Detergents and EmulsifiersAnnual."

By "agronomically acceptable carrier" is meant any substance which canbe utilized to dissolve, disperse or duffuse the chemical incorporatedtherein without impairing the effectiveness of the toxic agent and whichdoes no permanent damage to such environment as soil, equipment, andagronomic crops.

The phosphoramidate can be taken up on or mixed with a finely particledsolid carrier, as for example, clays, inorganic silicates, carbonates,and silicas.

Organic carriers can also be employed. Dust concentrates are commonlymade wherein phosphoramidates are present in the range of about 20 toabout 80%. For ultimate applications, these concentrates are normallyextended with additional solid to give an active ingredient content offrom 1 to about 20%. Granular formulations are made using a granular orpelletized form of carrier, such as granular clays, vermiculite,charcoal or corn cobs, and may contain the active ingredient in fromabout 1 to about 25% by weight.

Wettable powder formulations are made by incorporating the compounds ofthis invention in an inert, finely divided solid carrier along with asurfactant which can be one or more emulsifying, wetting, dispersing, orspreading agents or a blend of these. The phosphoramidates are usuallypresent in the range of about 10 to about 80% by weight and surfactantsin from about 0.5 to about 10% by weight. Commonly used emulsifying andwetting agents include polyoxyethylated derivatives of alkylphenols,fatty alcohols, fatty acids, alkylamines, alkylarene sulfonates anddialkyl sulfosuccinates. Spreading agents include such materials asglycerol mannitan laurate and a condensate of polyglycerol and oleicacid modified with phthalic anhydride. Dispersing agents include suchmaterials as the sodium salt of the copolymer of maleic anhydride and anolefin such as diisobutylene, sodium lignin sulfonate and sodiumformaldehydenaphthalene sulfonates.

One convenient method for preparing a solid formulation is to impregnatethe phosphoramidate onto the solid carrier by means of a volatilesolvent, such as acetone. In this manner, adjuvants, such as activators,adhesives, plant nutrients, synergists and various surfactants can alsobe incorporated.

Emulsifiable concentrate formulations are prepared by dissolving thephosphoramidates of this invention in an agronomically acceptableorganic solvent and adding a solvent soluble emulsifying agent. Suitablesolvents are usually water-immersible and can be found in thehydrocarbon, chlorinated hydrocarbon, ketone, ester, alcohol and amideclasses of organic solvents. Mixtures of solvents are commonly employed.The surfactants useful as emulsifying agents can constitute about 0.5 toabout 10% by weight of emulsifiable concentrates and can be anionic,cationic or non-ionic in character. The concentration of the activeingredients can vary from about 10 to about 80%, preferably in the rangeof about 25 to about 50%.

For use as pesticidal agents, these compounds should be applied in aneffective amount sufficient to exert the desired pesticidal activity bytechniques well known in the art. In certain situations, however, it maybe desirable and advantageous to apply the phosphoramidate directly ontothe loci to be protected or freed of pests without the benefit of anysubstantial amount of carrier. This is a particularly effective methodwhen the physical nature of the toxicants is such as to permit what isknown as "low-volume" application, that is, when the compounds are inliquid form or substantially soluble in higher boiling solvents.

The application rate will, of course, vary depending upon the purposesfor such application, the phosphoramidate being utilized, the frequencyof dissemination, and the like.

Many of the above formulations can be utilized on animals for thecontrol of parasites.

For use as arthropodicides, e.g. acaricides and insecticides, dilutesprays can be applied at concentrations of about 0.01 to about 20 poundsof the active ingredient per 100 gallons of spray. They are usuallyapplied at about 0.1 to about 5 pounds per 100 gallons. In moreconcentrated sprays, the active ingredient is increased by a factor of 2to 40. With dilute sprays, applications are usually made to the plantsuntil run-off is achieved, whereas with more concentrated or low-volumesprays, the materials are applied as mists.

For use as soil insecticides or as nematocides, the phosphoramidates canbe applied as a diluted liquid preparation or as a solid formulation,preferably a granular formulation, by broadcasting, side-dressing,introduction into the seed furrow, soil incorporation, or seedtreatment. The application rate can be from about 1 to about 50 poundsper acre of active ingredient and for economic reasons, preferably fromabout 1 to about 25 pounds per acre.

The compounds of this invention can be utilized as the sole pesticidalagents or they can be employed in conjunction with other bactericides,fungicides, herbicides, insecticides, acaricides, and comparablepesticides.

Many variations of this invention are possible without departing fromthe spirit or scope thereof.

We claim:
 1. A method of controlling pests which comprises applyingdirectly to the pests or to the loci to be freed of or protected fromattack by such pests, a pesticidally effective amount of a compound ofthe formula ##STR9## wherein R¹ is a (C₆ -C₁₀) aryl group, optionallysubstituted with up to five (C₁ -C₄) alkyl groups, (C₁ -C₄) alkoxylgroups, (C₁ -C₄) alkylthio groups; (C₁ -C₄) alkylsulfonyl groups, (C₁-C₄) hydroxyalkyl groups, (C₁ -C₄) haloalkyl groups, cyano groups, nitrogroups, hydroxyl groups, or halogen atoms;R³ is a (C₁ -C₆) alkyl group;R⁴ is a (C₃ -C₄) alkyl group; X is .[.an oxygen or.]. .Iadd.a.Iaddend.sulfur atom; Y is an oxygen or sulfur atom; and Z is an oxygenor sulfur atom and the agronomically acceptable metal sales and metalsalt complexes thereof.
 2. A compound of the formula: ##STR10## whereinA is independently(a) a (C₁ -C₄) alkyl group; (b) a (C₁ -C₄) alkoxygroup; (c) a (C₁ -C₄) alkylthio group; (d) a trihalomethyl group; or (e)a halogen atom; R⁵ is a (C₁ -C₄) alkylthio group or a (C₁ -C₄) alkoxygroup; R⁶ is a (C₃ -C₄) alkyl group; X is .[.an oxygen or.]. .Iadd.a.Iaddend.sulfur atom; and n is an integer from 0 to 3 and theagronomically acceptable metal salts and metal salt complexes thereof.3. A compound according to claim 2 whereinA is independently(a) a methylgroup; (b) a methoxy group; (d) a trifluoromethyl group; or (e) achlorine atom; R⁵ is a propylthio group or an ethoxy group; R⁶ is an-propyl, isobutyl, or sec-butyl group; X' is .[.an oxygen or.]. .Iadd.a.Iaddend.sulfur atom; and n is an integer of 0 to
 2. 4. A compoundaccording to claim 3 wherein R⁵ is an ethoxy group and R⁶ is an isobutylgroup or a sec-butyl group. .[.5. A compound according to claim 4 havingthe formula: ##STR11## .[.6. A compound according to claim 4 having theformula: ##STR12##
 7. A compound according to claim 4 having theformula: ##STR13## .[.8. A compound according to claim 5 having theformula: ##STR14## .[.9. A compound according to claim 5 having theformula: ##STR15##
 10. A pesticidal composition comprising a compoundaccording to claim 1 and an agronomically acceptable carrier.
 11. Amethod of controlling pests which comprises applying directly to thepests or to the loci to be freed of or protected from attack by suchpests, a pesticidally effective amount of the composition of claim 10.12. A method according to claim 11 wherein the pests are arthropods. 13.A method according to claim 12 wherein the arthropods are insects oracarids.
 14. A method according to claim 11 wherein the pests arenematodes.